Hydroformylation of 1-butene to N-pentanal on Co-based Materials Derived from ZIF-67: Optimization of Pyrolysis Conditions and DFT Study

Graphical We prepared the Co-based materials via the pyrolysis of ZIF-67 at low temperature, and obtained the optimum catalyst ZIF-67-Sg-350-10 with the conversion of 1-butene, aldehyde selectivity and n/i ratio of 94.9 %, 77.1 % and 2.2, respectively. We prepared the Co-based materials via the pyrolysis of ZIF-67 at low temperature (250 °C~350 °C), and obtained the optimum catalyst ZIF-67-Sg-350-10 with the conversion of 1-butene, aldehyde selectivity and n/i ratio of 94.9 %, 77.1 % and 2.2, respectively. The conversion of 1-butene and aldehyde selectivity obviously increased with the increasing pyrolysis temperature and pyrolysis time. It was found that the interaction between the Co cluster and N-doped carbon composites could improve the hydroformylation activity. Different catalyst models were built to investigate the active centers (Co) in the derived materials. The Co-N4 surface was the best catalyst model with the lowest hydrogen insertion reaction energy barrier (0.37 eV).